CN102516433A - Method for preparing cyclic olefin addition polymer of high gas permeability - Google Patents

Method for preparing cyclic olefin addition polymer of high gas permeability Download PDF

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CN102516433A
CN102516433A CN2011103408818A CN201110340881A CN102516433A CN 102516433 A CN102516433 A CN 102516433A CN 2011103408818 A CN2011103408818 A CN 2011103408818A CN 201110340881 A CN201110340881 A CN 201110340881A CN 102516433 A CN102516433 A CN 102516433A
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cycloolefin
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若槻康雄
手塚裕昭
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
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    • C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
    • C08J2343/04—Homopolymers or copolymers of monomers containing silicon

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Abstract

Provided is a method for preparing a cyclic olefin addition polymer of high gas permeability, which method including subjecting a specific type of cyclic olefin-functional siloxane and a mixture thereof with a specific type of cyclic olefin compound to addition polymerization in the presence of a multi-component catalyst containing (A) a zero-valent palladium compound, (B) an ionic boron compound, and (C) a phosphine compound having a substituent group selected from an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group and an aryl group, to obtain a cyclic olefin addition polymer of high gas permeability wherein a ratio of the structural units derived from the cyclic olefin-functional siloxane is at 10 to 100 mole% of the addition polymer and a number average molecular weight (Mn) ranges from 100,000 to 2,000,000.

Description

The method of the cycloolefin addition polymer that the preparation gas permeability is high
Technical field
The present invention relates to the cycloolefin addition polymer, more specifically, relate to preparation and have the method for particular type organo-siloxane as the high cycloolefin addition polymer of the gas permeability of side chain.
Background technology
In recent years, air-conditioning provides comfortable live and work space, and the visual plant that it has not only become office building and resident room also becomes the necessaries that delivers and transport instrument such as automobile, railway carriage, boats and ships and aircraft.Usually, use the environment high of air-conditioning airtight so that improve Energy efficiency.Therefore, if people work in such enclosed space continuously, will reduce owing to anoxic makes working efficiency.Especially for delivering and transporting instrument, safety-problems might appear such as causing lethargy.Make that stoping oxygen concentration to reduce becomes possibility although open the window, such opening will cause power loss and allow pollen, yellow sand, dust to get into, and harm environmental amenity property thus.Under these circumstances, developed and used and selectivity to pass through the air-conditioning of the oxygen permeable membrane of oxygen, but still can't realize satisfactory performance.
Organopolysiloxane is known as the excellent material of oxygen perviousness.Yet the physical strength of organopolysiloxane itself is low, in practical application, exists problem.In order to overcome this problem, proposed to adopt the multipolymer (patent documentation 1:JP-B H04-001652) and the ZGK 5/aromatic polyamide based block copolymer (patent documentation 2:JP-A H05-285216) of polycarbonate.Yet it is very complicated but also owing to they lack the difficult problem of permanent stability to the susceptibility of hydrolysis to have not only their preparation.
In addition; The various substituent polymkeric substance of organosilicon that have have been proposed; For example comprise: siliceous styrene derivatives (patent documentation 3:JP-A H04-88004); Siliceous anti-stilbenes verivate (patent documentation 4:JP-A H08-198881) and siliceous Mierocrystalline cellulose (patent documentation 5:JP-A 2001-79375).About these polymkeric substance of oxygen perviousness is gratifying, but thermostability and physical strength also can't be satisfactory.
In patent documentation 6 (JP-A 2007-291150), propose to have organo-siloxane as the cycloolefin ring-opening polymerization polymer of side chain and its hydrogenate.Yet these polymkeric substance have problems aspect thermotolerance and film toughness under most of situation, and are attended by because their depolymerization ability makes them lack the problem of permanent stability.
Aspect the cyclic olefins polyaddition reaction, (JP 3476466 for patent documentation 7-22:JP-A H04-63807 and JP-A H08-198919, JP-A H09-508649 many suggestions once to occur; JP-AH07-196736, WO 199720871, and WO 199820394, and JP 3801018; WO 2002062859, JP-A2003-252881, and DE-OS 4128932; JP-A 2007-77252 and JP-A2007-70337, JP4075789, WO 2007069518 and JP-A 2008-202003).Yet, do not mention the monomer of cycloolefin functionality siloxanes as polyaddition reaction.Certainly, in fact containing siloxanes never reported as the example of the addition polymer of repeating unit.
In the patent documentation of just having mentioned 7 to 22, described the development that the cycloolefin addition polymer is applied to optics and electronic unit in detail, their heat of special concern simultaneously, kinetics, optics and electronic property.But, the not application of report concern gas permeability aspect.
Recently, in patent documentation 23 (JP-A 2009-173824) and patent documentation 24 (JP-A2009-249610), reported the addition polymer that in structure, contains cycloolefin functionality siloxane repeat unit.Although the polymkeric substance that in these applications, proposes shows excellent resolvability, they do not have physical strength and the gas permeability of enough standing practical application.Especially, the polymkeric substance that in back one piece of patent documentation 24, proposes, when the amount of the organo-siloxane side chain of the gas permeability of giving polymkeric substance increased, physical strength significantly descended.This is owing to when the monomer that reacts as addition polymer with cycloolefin functionality siloxanes, can't obtain the polymkeric substance that molecular weight is enough to guarantee physical strength, and this is illustrated in all some difficult problems to be solved of the preparation method that proposed in patent documentation 23 and 24.
The prior art document is listed below.
Quote catalogue
Patent documentation 1:JP-B H04-001652
Patent documentation 2:JP-A H05-285216
Patent documentation 3:JP-A H04-88004
Patent documentation 4:JP-A H08-198881
Patent documentation 5:JP-A 2001-79375
Patent documentation 6:JP-A 2007-291150
Patent documentation 7:JP-A H04-63807
Patent documentation 8:JP-A H08-198919
Patent documentation 9:JP-A H09-508649
Patent documentation 10:JP 3476466
Patent documentation 11:JP-A H07-196736
Patent documentation 12:WO 199720871
Patent documentation 13:WO 199820394
Patent documentation 14:JP 3801018
Patent documentation 15:WO2002062859
Patent documentation 16:JP-A 2003-252881
Patent documentation 17:DE-OS 4128932
Patent documentation 18:JP-A 2007-77252
Patent documentation 19:JP-A 2007-70337
Patent documentation 20:JP 4075789
Patent documentation 21:WO 2007069518
Patent documentation 22:JP-A 2008-202003
Patent documentation 23:JP-A 2009-173824
Patent documentation 24:JP-A 2009-249610
Patent documentation 25:JP 3534127
Patent documentation 26:WO 200020472
Patent documentation 27:US 6455650
Patent documentation 28:JP-A H05-262821
Non-patent literature 1:Macromol.Symp.89,433-442 (1995)
Summary of the invention
The present invention makes under these situation in the prior art; The method that the purpose of this invention is to provide the high cycloolefin addition polymer of preparation gas permeability accordingly; Said addition polymer has excellent gas permeability and high thermal stability and physical strength, has excellent solvent simultaneously and is prone to solvability.
We have carried out deep research to realize above-mentioned target; The result finds; In the presence of the multicomponent catalyst of compound (A) below the containing of particular type, (B), (C); Mixture through with the cyclic olefins of this cycloolefin functionality siloxanes of the cycloolefin functionality siloxanes of following formula (1) or formula (1) and following formula (2) carries out the cycloolefin addition polymer that addition polymerization obtains having ad hoc structure; Wherein said cycloolefin addition polymer has the structural unit from the cycloolefin functionality siloxanes of formula (1) of the 10-100mol% ratio of addition polymer; Be the number-average molecular weight (Mn) of 100000～2000000 scopes through using THF (being abbreviated as THF here) as the polystyrene conversion of the gpc measurement of solvent, and it demonstrates excellent oxygen permeability, thermotolerance, physical strength and solvability.The present invention is based on this discovery.
The wide aspect according to the present invention; More particularly provide preparation to have high gas permeability and with respect to the method for polystyrene standards by the cycloolefin addition polymer of 100000～2000000 number-average molecular weight (Mn) of gel permeation chromatography; This method is included in and comprises the ionic boron compound of (A) 0 valency palladium compound, (B) and exist down with the multicomponent catalyst that (C) has the substituent phosphine compound that is selected from alkyl, cycloalkyl and aryl with 3 to 6 carbon atoms; Addition polymerization is by the cycloolefin functionality siloxanes of the cycloolefin functionality siloxanes of following formula (1) expression or formula (1) with by the mixture of the cyclic olefins of following formula (2) expression; Obtain the cycloolefin addition polymer thus; Wherein the construction unit from the cycloolefin functionality siloxanes of formula (1) is the 10mol% to 100mol% of this addition polymer
R wherein 1Can be identical or different, and the unit price organic group of expression not fatty family unsaturated link(age), s is 0 to 2 integer, and j is 0 or 1,
A wherein 1To A 4Independently expression be selected from Wasserstoffatoms, halogen atom, have alkyl, thiazolinyl, naphthenic base, aryl, alkoxyl group, aryloxy and the halo alkyl of 1 to 10 carbon atom group, or be selected from the polar group of oxetanyl and carbalkoxy, condition is A 1And A 2Perhaps A 1And A 3Can form alicyclic structure, aromatic ring structure, carbimide (carbonimide) group or anhydride group with the carbon atom of their institute's bondings, and i is 0 or 1.
In the method, preferably: compound (A) is two (dibenzalacetone) palladiums, and it is the complex compound that two dibenzalacetone molecules cooperate with one 0 valency palladium atom; Perhaps be three (dibenzalacetones), two palladiums; It is the complex compound that three dibenzalacetone molecules cooperate with two 0 valency palladium atoms; Compound (B) is triphenylcarbenium four (pentafluorophenyl group) borate or four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound, and compound (C) is a tricyclohexyl phosphine.
The R in the formula (1) further preferably 1Be methyl.
Preferably, the A in the formula (2) 1To A 4Independent expression Wasserstoffatoms and i are 0.
Polyaddition reaction is preferably carrying out under the condition 0-150 ℃ and 1 to 72 hour under the non-active gas atmosphere.
Preferably; Calculate with 0 valency palladium; Compound (A) uses with 1/1000000 to 1/100 mole amount with respect to every mole of formula (1) and the monomeric total amount of formula (2); Compound (B) uses with the amount of 1.0-2.0 mole with respect to every mole compound (A), and compound (C) uses with 0.25 to 2.0 mole amount with respect to every mole compound (A).
Further preferably, polyaddition reaction carries out in solvent, and wherein the amount S of solvent representes the scope 0.1 to 30 with the weight ratio of the total amount M of the cycloolefin monomers of being made up of the compound of formula (1) and formula (2) with S/M.
Beneficial effect of the present invention
According to the present invention, the vinyl addition polymerization through cycloolefin in the presence of the multicomponent catalyst of particular type can make polymkeric substance easily.The polymkeric substance that obtains has excellent gas permeability, and particularly excellent oxygen perviousness has high thermal stability (thermotolerance) and film toughness (physical strength) and the excellent solvability in organic solvent simultaneously.
The accompanying drawing summary
Fig. 1 is the figure of relation that the productive rate of the polymkeric substance that obtains among temperature of reaction and the embodiment 1 to 5 is shown;
Fig. 2 is the figure of relation that the molecular weight of the polymkeric substance that obtains among temperature of reaction and the embodiment 1 to 5 is shown;
Fig. 3 is the figure of relation that the MWD of the polymkeric substance that obtains among temperature of reaction and the embodiment 1 to 5 is shown;
Fig. 4 illustrates temperature of reaction and the figure of the relation of the productive rate of the polymkeric substance that in embodiment 6,7 and comparative example 1 to 4, obtains;
Fig. 5 is the figure of relation that the productive rate of the polymkeric substance that obtains among temperature of reaction and the embodiment 8 to 13 is shown;
Fig. 6 is the polymer P (7) that obtains among the embodiment 7 1H-NMR figure; And
Fig. 7 is the polymer P (14) that obtains among the embodiment 10 1H-NMR figure.
Embodiment
According to the cycloolefin addition polymer of high gas permeability of the present invention is that the addition polymerization through the cyclic olefins represented by the cycloolefin functionality siloxanes of the cycloolefin functionality siloxanes of formula (1) expression or formula (1) expression and formula (2) obtains in the presence of multicomponent catalyst, and described multicomponent catalyst comprises following compound (A), (B) and (C):
Compound (A) is 0 valency palladium compound;
Compound (B) is ionic boron cpd;
Compound (C) is to have the substituent phosphine compound that is selected from the alkyl, naphthenic base and the aryl that contain 3 to 6 carbon atoms.
As the conventional polyaddition reaction catalyzer of cyclic olefins; Can enumerate transition metal complex; Its central metal is selected from the element of the periodic table of elements the 8th, 9 and 10 families, for example comprises iron (Fe), cobalt (Co), nickel (Ni), rubidium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt).Yet for obtaining the cycloolefin addition polymer with excellent physical properties of the present invention, requirement has the high-molecular weight product by the reactive high and polymkeric substance that obtain of the cycloolefin functionality siloxanes of formula (1) expression.From this viewpoint, need to have as the compound (A) of the part of the palladium of central metal and particular type, ionic boron cpd (B) and make up use with phosphine compound (C).
In addition, central metal is that the compound (A) of palladium need be 0 valency palladium compound.As mentioned below, cycloolefin addition polymer of the present invention is characterised in that it is based on and prepares from the polymerization activity of the excellence of using 0 valency palladium compound and molecular-weight adjusting function.
So far, the palladium compound of having reported that is used for the cycloolefin addition polymerization (referring to patent documentation 7 to 24) all uses the palladium of divalence, and uses the cycloolefin addition polymerization of 0 valency palladium compound also not report.In patent documentation 25, although given an example some 0 valency palladium compounds, they are only given an example, and the practical application to them is not described in detail.In patent documentation 26, a polymerization example that uses two (tricyclohexyl phosphine) palladium compounds has only been proposed in embodiment 289.Yet, not only do not mention the productive rate of the polymkeric substance that obtains, and do not mention its molecular weight yet.These facts show do not find also in the prior art that hereinafter details by (A) 0 valency palladium compound, (B) the ionic boron cpd and (C) excellent properties of the multicomponent catalyst of phosphine compound preparation.
Compound (A)
Compound (A) comprises palladium as central metal, and palladium is the element of the periodic table of elements the 10th family, especially the palladium compound of 0 valency.Concrete example comprises: two (dibenzalacetone) palladium, and to be two dibenzalacetone molecules (perhaps 1,5-phenylbenzene-1,4-pentadiene-3-ketone, it is abbreviated as aba sometimes) with one 0 valency palladium atom cooperate and the complex compound that forms for it; Three (dibenzalacetones), two palladiums, to be three dibenzalacetone molecules with two 0 valency palladium atoms cooperate and the complex compound that forms for it; (ethylidene) two (tricyclohexyl phosphine) palladium, to be ethylidene unit and two thricyclohexyl phosphine groups with one 0 valency palladium atom cooperate and the complex compound that forms for it; Carbonyl three (triphenylphosphine) palladium, it is to be cooperated with one 0 valency palladium atom and the complex compound that forms by carbon monoxide unit and three triphenyl phosphorus groups; Two (isocyano-uncle butane) palladiums etc., it is that two tertiary butyl isocyanide groups and one 0 valency palladium atom cooperate and the complex compound of formation.Wherein, consider easy processing property, operability and the stability of complex compound, preferred two (dibenzalacetone) palladium and three (dibenzalacetone) two palladiums.
Compound (B)
Compound (B) is ionic boron cpd.Concrete example comprises: triphenylcarbenium
Figure BSA00000604139200071
four (pentafluorophenyl group) borate, triphenylcarbenium
Figure BSA00000604139200072
four [3; Two (trifluoromethyl) phenyl of 5-] borate, N; Accelerine four (pentafluorophenyl group) borate and four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound.Wherein, consider the solvability of complex compound in organic solvent and the simple preferred triphenylcarbenium of availability
Figure BSA00000604139200073
four (pentafluorophenyl group) borates and four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound.
Compound (C)
Compound (C) is a phosphine compound, and it has the substituted radical that is selected from alkyl, naphthenic base and aryl with 3-6 carbon atom.Concrete example comprises: tri isopropyl phosphine, tri-butyl phosphine, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine, di-tert-butyl-phenyl phosphine etc.Wherein, tricyclohexyl phosphine is owing to satisfy catalytic activity with stable but preferred simultaneously.
According to of the present invention one preferred embodiment; The cycloolefin addition polymer of high gas permeability prepares through using following substances: as compound (A); Two (dibenzalacetone) palladiums or three (dibenzalacetones), two palladiums; As compound (B); Triphenylcarbenium four (pentafluorophenyl group) borates or four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound, and as compound (C), tricyclohexyl phosphine.
Preferred embodiment is described below.
I. compound (A) is two (dibenzalacetone) palladiums; To be two dibenzalacetone molecules with one 0 valency palladium atom cooperate and the complex compound that forms for it; Compound (B) is triphenylcarbenium
Figure BSA00000604139200075
four (pentafluorophenyl group) borate, and compound (C) is a tricyclohexyl phosphine.
Ii. compound (A) is to get (dibenzalacetone) palladium; To be two dibenzalacetone molecules with one 0 valency palladium atom cooperate and the complex compound that forms for it; Compound (B) is four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound, and compound (C) is a tricyclohexyl phosphine.
Iii. compound (A) is three (dibenzalacetones), two palladiums; To be three dibenzalacetone molecules with two 0 valency palladium atoms cooperate and the complex compound that forms for it; Compound (B) is triphenylcarbenium
Figure BSA00000604139200076
four (pentafluorophenyl group) borate, and compound (C) is a tricyclohexyl phosphine.
Iv. compound (A) is three (dibenzalacetones), two palladiums; To be three dibenzalacetone molecules with two 0 valency palladium atoms cooperate and the complex compound that forms for it; Compound (B) is four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound, and compound (C) is a tricyclohexyl phosphine.
The high cycloolefin addition polymer of gas permeability according to the present invention through by above-claimed cpd (A), (B) and (C) in the presence of the formed multicomponent catalyst, will prepare by the represented cycloolefin functionality siloxanes of following formula (1) or the cycloolefin functionality siloxanes and the represented cyclic olefins addition polymerization of following formula (2) of formula (1).
Figure BSA00000604139200081
R wherein 1Can be identical or different, the unit price organic group of expression not fatty family unsaturated link(age), s representes 0 to 2 integer, and j is 0 or 1,
Figure BSA00000604139200082
A wherein 1To A 4Expression is selected from Wasserstoffatoms, halogen atom, has the group of alkyl, thiazolinyl, naphthenic base, aryl, alkoxyl group, aryloxy and the halo alkyl of 1 to 10 carbon atom independently, perhaps is selected from the polar group of oxetanyl and carbalkoxy, and condition is A 1And A 2Perhaps A 1And A 3Can form alicyclic structure, aromatic ring structure, carbimide group or anhydride group with the carbon atom of their institute's bondings, and i is 0 or 1.
In following formula (1), R 1Can be identical or different; And the unit price organic group of the not fatty family of expression unsaturated link(age); Preferred unsubstituted or substituted univalence hydrocarbyl with 1-10 carbon atom; For example, alkyl such as methyl, ethyl, n-propyl, butyl, amyl group etc., aryl such as phenyl, tolyl, xylyl etc.; Aralkyl adds phenmethyl, 2-phenylethyl, 3-phenyl propyl etc., and 1 or more a plurality of Wasserstoffatomss are by substituted groups such as halogen atom such as fluorine atom, chlorine atom, bromine atoms in the perhaps above-mentioned group.
As the cycloolefin functionality siloxanes of formula (1) expression, the following compound of in practical application of the present invention, can giving an example out, but be not limited to these object lessons.In these formulas, Me representes methyl, and Ph representes phenyl (hereinafter no matter when occur, Me and Ph have same implication respectively).
Figure BSA00000604139200091
The cycloolefin functionality siloxanes of formula (1) can use separately or two kinds or more kinds of combination use.
R 1Be methyl, the cycloolefin functionality siloxanes of the formula of j=0 and s=0 (1) for example can be according to following step preparation.
In the first step, said siloxanes can prepare according to Diels-Alder reaction between represented siloxanes with terminal olefine of reactions formula and the Dicyclopentadiene (DCPD).
Figure BSA00000604139200092
In second step, capable of using at norbornadiene in the presence of the palladium catalyst with contain the addition reaction between the functionality siloxanes of SiH group accordingly.
Figure BSA00000604139200093
In following formula (2), A wherein 1To A 4Expression is selected from Wasserstoffatoms independently, and halogen atom such as fluorine atom, chlorine atom, bromine atoms etc. have alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, octyl group, nonyl, the decyl of 1 to 10 carbon atom etc.; Thiazolinyl such as vinyl, allyl group, crotonyl, hexenyl etc.; Naphthenic base such as cyclohexyl etc., aryl such as phenyl, tolyl, xylyl, naphthyl etc., alkoxyl group such as methoxyl group, oxyethyl group, propoxy-etc.; Aryloxy such as phenoxy etc.; With the halo alkyl as 3,3,3-trifluoro propyl, 2-(perfluoro butyl) ethyl, 2-(perfluoro capryl) ethyl, to the group of stupid base of chlorine etc.; Perhaps be selected from the polar group of oxetanyl and carbalkoxy; The alkoxyl group part of said carbalkoxy preferably has 1-10 carbon atom, more preferably 1-6 carbon atom, for example methoxycarbonyl, tertbutyloxycarbonyl etc.In addition, A 1And A 2Perhaps A 1And A 3Can form alicyclic structure with the carbon atom of their bondings, aromatic ring structure, carbimide group or acid anhydrides.
In this case, the alicyclic structure in the formula (2) comprises the alicyclic structure with 4-10 carbon atom, and aromatic ring structure comprises those aromatic ring structures with 6-12 carbon atom.The instance of these structures is for being described below.
The alicyclic structure aromatic ring structure
Figure BSA00000604139200101
Carbimide group anhydride group
Figure BSA00000604139200102
Should be noted that structure that these and norbornylene ring key close or examples of groups be following in formula (2) those of i=0.
The alicyclic structure aromatic ring structure
Figure BSA00000604139200103
Carbimide group anhydride group
Figure BSA00000604139200104
Include but not limited to following those by the represented cyclic olefins of formula (2).
Concrete example comprises: dicyclo [2.2.1] hept-2-ene", 5-methyl-dicyclo [2.2.1] hept-2-ene", 5-ethyl-dicyclo [2.2.1] hept-2-ene", 5-propyl group-dicyclo [2.2.1] hept-2-ene"; 5-butyl-dicyclo [2.2.1] hept-2-ene", 5-amyl group-dicyclo [2.2.1] hept-2-ene", 5-hexyl-dicyclo [2.2.1] hept-2-ene", 5-octyl group-dicyclo [2.2.1] hept-2-ene"; 5-decyl-dicyclo [2.2.1] hept-2-ene", 5-phenyl-dicyclo [2.2.1] hept-2-ene", 5-vinyl-dicyclo [2.2.1] hept-2-ene", 5-allyl group-dicyclo [2.2.1] hept-2-ene"; 5-isopropylidene-dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl-dicyclo [2.2.1] hept-2-ene", 5-fluoro-dicyclo [2.2.1] hept-2-ene"; 5-chloro-dicyclo [2.2.1] hept-2-ene", dicyclo [2.2.1] heptan-5-alkene 2-formic acid methyl ester, dicyclo [2.2.1] heptan-5-alkene-2-formic acid ethyl ester; Dicyclo [2.2.1] heptan-5-alkene-2-formic acid butyl ester, 2-methyl-dicyclo [2.2.1] heptan-5-alkene-2-formic acid methyl ester, 2-methyl-dicyclo [2.2.1] heptan-5-alkene-2-formic acid ethyl ester; 2-methyl-dicyclo [2.2.1] heptan-5-alkene-2-formic acid propyl diester, 2-methyl-dicyclo [2.2.1] heptan-5-alkene-2-methanoic acid trifluoro ethyl ester, 2-methyl-dicyclo [2.2.1] hept-2-ene" guanidine-acetic acid ethyl ester; 2-methyl-dicyclo [2.2.1] heptan-5-thiazolinyl propenoate, 2-methyl-dicyclo [2.2.1] heptan-5-thiazolinyl methacrylic ester, dicyclo [2.2.1] heptan-5-alkene-2; 3-dioctyl phthalate dimethyl esters, three ring [4.3.0.12,5] ten-3-alkene; Fourth Ring [4.3.0.12,5.17,10] 12-3-alkene etc.They can use separately or two or more combination is used.
Thermotolerance and oxidative degradation property from the polymkeric substance that obtains preferably do not contain unsaturated link(age) by the represented cyclic olefins of formula (2) in its structure.Situation for the addition polymerization of the compound that comprises unsaturated link(age) such as 5-vinyl-dicyclo [2.2.1] hept-2-ene"; Carbon-carbon double bond on the side chain of the polymkeric substance that obtains preferably should experience hydrogenation or hydrosilylation, because this can improve thermotolerance and oxidative degradation property.
If the cyclic olefins by formula (2) expression comprises polar group such as ester group, the polymkeric substance that obtains is being improved to the binding property of adherend or the solvability in organic solvent, but has the trend that reduces gas permeability.Therefore, the suitable selection according to purpose is favourable.
Feed ratio between the cyclic olefins of the cycloolefin functionality siloxanes of formula (1) and formula (2) preferably uses by this way: when considering the gas permeability of the cycloolefin addition polymer that the present invention obtains, from the structural unit of formula (1) compound be 10-100 mole % in polymkeric substance, more preferably in the 20-100 mole % scope.
The compound of multicomponent catalyst (A), (B), (C) use with the amount of following ranges respectively.
In 0 valency palladium, with respect to every mole of formula (1) and (2) monomeric total amount, compound (A) preferably 1/1000000 to 1/100 mole, more preferably in 1/100000 to 1/1000 mole the scope.If compound (A) uses with bigger amount, might can not get having the polymkeric substance of expection molecular weight.The amount of less usefulness will cause polymerization activity to reduce under some situation.
With respect to every mole compound (A), compound (B) is preferably 1.0 to 2.0 moles, more preferably 1.0 to 1.5 moles.The amount of bigger compound (B) possibly make it residual in the polymkeric substance that obtains, thereby may be painted.Less amount possibly reduce polymerization activity.
With respect to every mole compound (A), compound (C) is preferably 0.25 to 2.0 mole, more preferably 0.5 to 1.5 mole.The amount of bigger compound (C) possibly reduce polymerization activity, and less amount possibly reduce the stability of catalyzer.
The high cycloolefin addition polymer of gas permeability of the present invention can through mentioned above by compound (A), (B) and the multicomponent catalyst that (C) forms in the presence of in one or more solvents polymerization prepare; Said solvent is selected from alicyclic hydrocarbon type solvent such as hexanaphthene, pentamethylene etc.; Aliphatic hydrocarbon kind solvent such as hexane, octane etc.; Aromatic hydrocarbon solvent such as toluene, benzene, YLENE etc.; Halogenated hydrocarbon solvent such as methylene dichloride, zellon, chlorobenzene etc. and cyclopolysiloxane solvent such as octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane etc.
When the scale of solvent was shown the weight ratio (S/M) of solvent (S) and cycloolefin monomers (M) (total amount of the compound of above-mentioned formula (1) and (2)), it was 0.1 to 30, in preferred 1 to 20 the scope.If the amount of solvent is during less than aforementioned proportion, soltion viscosity increases and maybe difficult treatment.On the other hand, when this amount surpasses aforementioned proportion, the polymerization activity possible deviation.
When mixing contacting with cycloolefin monomers by the multicomponent catalyst that compound (A), (B), (C) form; Can comprise several working method; Comprise working method 1; Wherein, compound (A) is dissolved in solution input in the aforesaid solvent by compound (B) and (C), mix in the solution of the solvent composition of cycloolefin monomers and the above-mentioned type and with it; Working method 2 wherein, with compound (A) and (C) is dissolved in solution input in the aforesaid solvent by mixing in the solution of the solvent composition of compound (B), cycloolefin monomers and above-mentioned use and with it; Working method 3 wherein, is mixed compound (A), (B) and the solution input that (C) is dissolved in the aforesaid solvent by the solution of the solvent of cycloolefin monomers and above-mentioned use and with it.Consider preferred method of operation 3 from the effective generation aspect that allows the catalytic activity kind.
In the preparation method of cycloolefin addition polymer of the present invention, temperature of reaction is important.This is because when using the multicomponent catalyst that is formed by compound (A), (B), (C), the molecular weight of the cycloolefin addition polymer that the present invention obtains can regulate suitably according to temperature of reaction.
For the method for the molecular weight of regulating the cycloolefin addition polymer that uses the palladium compound catalyzer, the past, known those methods comprised:
1) is transformed into the method (referring to non-patent literature 1) of low molecular weight product through the amount that increases catalyzer;
2) add the method (referring to patent documentation 10) of terminal olefin compound as molecular weight regulator;
3) add the method (referring to patent documentation 27) of cyclopentenes as molecular weight regulator;
4) add the method (referring to patent documentation 20) of ethene as molecular weight regulator; With
5) add the method (referring to patent documentation 28) of hydrogen as molecular weight regulator.
Yet, aforesaid method 1) and need a large amount of catalyzer, and at cost with from the polymkeric substance that obtains, remove catalyzer and have problems.In method 2) and 3) in regulate molecular weight mechanism for terminal olefin or cyclopentenes are incorporated into the polymkeric substance end of the chain, then carry out β-hydrogen separation.Usually, this effect of palladium catalyst is little, therefore needs to add a large amount of palladium catalysts.In method 4) and 5) in, relate to numerous industrial problem, because must introduce gas such as the ethene and the hydrogen of difficult treatment, although and depend on the feed pressure polymerization activity and still reduce.Although report, as usual method, molecular weight can be regulated through polymerization temperature, and regulating effect such when using known palladium catalyst so far is little.In addition, never there is report to clearly illustrate that effect itself.More specifically, make us quite surprised and what is interesting is that discovery can be through the molecular weight of temperature of reaction adjusting cycloolefin addition polymer of the present invention when passing through to use the multicomponent catalyst of being made up of compound (A), (B), (C).
Preferably; Polymerization method comprises: according in the aforesaid operations method any, in atmosphere such as non-active gas such as nitrogen, argon gas, initial monomers is dropped in the reaction vessel; And, carried out polymerization 1 to 72 hour, preferred 2 to 48 hours 0 to 150 ℃, the temperature of preferred 20 to 100 ℃ of scopes.Yet, for this, when temperature of reaction is too low, the polymerization activity possible deviation.Too high temperature possibly cause gelling, and is difficult to regulate molecular weight.
When using the multicomponent catalyst that forms by compound (A), (B), (C), do not need molecular weight regulator, but the regulating effect of molecular weight can be enhanced when using molecular weight regulator together.As such molecular weight regulator; Can enumerate hydrogen, terminal olefin such as ethene, butylene, 1-hexene, 1-octene etc.; Cycloolefin such as cyclopentenes, cyclooctene etc.; Aromatic vinyl compound such as vinylbenzene, 3-vinyl toluene, Vinylstyrene etc. and vinyl silicon compound are like three (trimethylammonium methoxyl group) vinyl silanes, divinyl two hydrogen silanes, vinyl cyclotetrasiloxane etc.
Usually be difficult to measure solvent and monomeric ratio, polymeric reaction temperature and polymerization reaction time.Should come suitably to use them according to the purpose of the polymkeric substance that will obtain to have the particular type structure.
Be selected from compounds such as water, alcohol, ketone, organic acid polymerization is stopped is feasible through use.When water and ethanol and acid are made an addition to polymers soln like the mixture of lactic acid, toxilic acid, oxalic acid etc., catalyst residue can separate from polymers soln and remove.In order to remove catalyst residue, can remove or remove through using gac, zeyssatite, alumina, silicon-dioxide etc. to adsorb with the strainer filtering separation.
Polymkeric substance can under reduced pressure obtain down at 60 to 150 ℃ through polymers soln being put into alcohol like cohesions such as methyl alcohol, ethanol etc. or ketone such as acetone, methylethylketones in dry 6 to 48 hours.In the method, catalyst residue and the unreacted monomer stayed in the polymers soln also are removed.Can easily remove the unreacted monomer that contains siloxanes that the present invention uses through using the mixed solvent of aforesaid alcohol or ketone and cyclopolysiloxane such as octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane etc.
The cycloolefin addition polymer of the present invention that obtains thus comprises the recurring group of following formula (3), and it is that cycloolefin functionality siloxanyl monomers addition polymerization through above-mentioned formula (1) forms,
Figure BSA00000604139200141
R wherein 1, s and j have respectively with formula (1) in identical implication.
When the cyclic olefins of use formula (2), cycloolefin addition polymer of the present invention contains the repeating unit of following formula (4), its be cyclic olefins through above-mentioned formula (2) addition polymerization forms as monomer,
A wherein 1To A 4Correspondingly has identical implication with i with formula (2).
Although when i is 0, A 1To A 4When all being Wasserstoffatoms, represent 2 by the repeating unit of formula (4) expression, 3-addition structural unit, possibly comprise also that the cyclic olefins of through type (2) forms as the monomer addition polymerization 2,7-addition structural unit.These structural units are applicable to the repeating unit by formula (3) representative.
In the ratio of the structural unit of the high cycloolefin addition polymer Chinese style (3) of gas permeability of the present invention normally at 10 to 100 moles of %, preferably at 20 to 100 moles of %.If the structural unit ratio of formula (3) is less than 10 moles of %, then gas permeability becomes and makes us dissatisfied.Especially; Consider from gas permeability, solvability and physical strength organic solvent; Preferably comprise 20 to 100 moles of % from the structural unit of formula (1) compound and comprise the structural unit of 0 to 80 mole of % from the compound of formula (2), separately based on cyclic olefins.If having the structural unit from formula (2) compound is the structural unit of formula (4), its amount is at least 0.1 mole of %.
The represented structural unit in formula (3) and (4) can randomly exist, and form that perhaps can block is present in the high cycloolefin addition polymer of gas permeability of the present invention.
The molecular weight of cycloolefin addition polymer of the present invention is the important factor that has influence on the excellent physical properties exploitation.Number-average molecular weight (Mn) is 100000～2000000, and preferably 150000 to 1500000, it is measured through the gel permeation chromatography (GPC) that uses the THS solvent with respect to PS.Ratio (the dispersity: Mw/Mn) preferably in 1.0 to 6.0 scope, more preferably in 1.0 to 5.5 scope of weight-average molecular weight (Mw) and number-average molecular weight (Mn).If the polymkeric substance that number-average molecular weight less than 100000, then obtains becomes fragile, and when forming film, film and sheet material, be easy to crackle.Therefore, can not get withstanding the film toughness of actual use.On the other hand, when number-average molecular weight surpassed 2000000, mouldable processibility and the solvability person of the being lowered into soltion viscosity in solvent uprised, and caused the processing property of difference.If the ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn) (dispersity: Mw/Mn) surpass 6.0, exist the polymkeric substance that obtains break and fragility aspect the situation of variation.In practical application of the present invention; When using the multicomponent catalyst that forms by compound (A), (B), (C), to such an extent as to will obtain narrow molecular weight distribution number-average molecular weight (Mn) easily 100000 to 2000000 and the cycloolefin addition polymer of ratio Mw/Mn in 1.0 to 6.0 scopes of weight-average molecular weight (Mw) and number-average molecular weight (Mn).This will finally cause fracture-resistant and anti-fragility excellent when forming coated film or film such as film or sheet material.
The second-order transition temperature of cycloolefin addition polymer of the present invention is measured through using TMS (thermo-mechanical analysis).The second-order transition temperature of estimating in this way preferably 200 to 400 ℃, more preferably at 220 to 380 ℃.If second-order transition temperature is lower than 200 ℃, then existence caused when processing or when using the molding comprise cycloolefin addition polymer of the present invention the possibility of thermal distortion.When second-order transition temperature surpassed 400 ℃, hot-work had under too high temperature, carry out, thereby the molding that contains cycloolefin addition polymer of the present invention maybe thermal degradation when.
The structure of cycloolefin addition polymer of the present invention can according to nuclear magnetic resonance spectrum ( 1H-NMR, 29Si-NMR) confirm.For example, can confirm structure as follows: 1During H-NMR analyzes (in deuterochloroform), from because of-O-Si (C 6H 5)-O--C 6H 5Absorption 7.8 to 6.5ppm, from cycloaliphates in 0.6 to 3.0ppm absorption, because of-Si-CH 2-,-Si-CH 3With-O-Si-CH 3Absorption 0.0 to 0.6ppm and because of-O-Si (CH 3)-O-is in-0.1 to 0.0 absorption, and 29During Si-NMR analyzes (deuterium for benzene in), from from the unitary absorption (R of M 3: methyl, 10.0 to 5.0ppm), from the unitary absorption (R of D 3: methyl ,-15.0 to 25.0ppm, R 3: phenyl ,-45.0 to-50.0ppm) and from T unit (R 3: alkyl ,-65.0 to-70.0), explain in following formula (5) with their integration ratio all unit.
Figure BSA00000604139200161
T unit, M cells D unit
R 3Have and the middle identical implication of R1 of formula (1).
The cycloolefin addition polymer that gas permeability of the present invention is high preferably uses with the shape of film, sheet material or film.The thickness of film, sheet material or film is not crucial, is generally adjusted to be in the scope of 10nm to 3mm according to purpose.Mode to forming film, sheet material or film does not specifically limit, and all forms easily through arbitrary method.Consider that from the angle that suppresses polymer deterioratoin through thermal history preferably the method (casting method) through solution casting forms, in the method with polymer dissolution of the present invention in solvent, be coated on the supporter, then that coating is dry; The WS casting method that is used for film wherein, falls to WS polymers soln of the present invention, and gets with the supporter handful; Perhaps dried wetting phase changes method, wherein, polymer dissolution of the present invention in solvent, and is coated to it on supporter, then it is immersed in the poor solvent.
At solution casting method, the solvent that uses in WS casting method and the dried wetting phase transformation method should be the solvent that can dissolve addition polymer of the present invention.Most of addition polymer of the present invention may be dissolved in the aliphatic solvents like pentamethylene, hexane, hexanaphthene, decane, Permethyl 99A. etc.; Aromatic hydrocarbon solvent such as toluene, YLENE, ethylbenzene etc.; Halogenated hydrocarbon solvent such as methylene dichloride, chloroform etc. and ZGK 5 solvent such as SWS-F 221, methyl three (trimethylsiloxy) silane, decamethylcyclopentaandoxane etc.These solvents can use separately also can two kinds or the use of more kinds of solvent combinations.Cycloolefin addition polymer of the present invention shows excellent solvability in above-mentioned arbitrary solvent, but depends on the thickness or the coating condition of film, and solvent residual when drying possibly not be removed.Therefore, the preferred use contained the solvent as staple such as the lower hexane of boiling point, hexanaphthene, toluene.
The oxygen permeability coefficient of the casting films of the cycloolefin addition polymer of the present invention that forms according to aforesaid method is measured through using pressure differential method.The oxygen perviousness of the cycloolefin addition polymer casting films of estimating by this way preferably is no less than 40 crust (1 crust=10 -10Cm 3(STP) .cm/cm 2.s.cmHg), more preferably be no less than 50 crust (1 crust=10 -10Cm 3(STP) .cm/cm 2.s.cmHg).If oxygen permeability coefficient is less than 40 crust (1 crust=10 -10Cm 3(STP) .cm/cm 2.s.cmHg), possibly there are some situations that can not get gratifying oxygen delivery performance.
Because the high cycloolefin addition polymer of gas permeability according to the present invention contains structural unit a high proportion of and from the corresponding formula (3) of the monomeric structural unit of formula (1); Therefore, it shows high solvability in Permethyl 99A. solvent or ZGK 5 solvent such as methyl three (trimethylsiloxy) silane, decamethylcyclopentaandoxane etc.Known, these solvents are little to the influence of human body and environmental pressure, and therefore these solvents have high security.This makes addition polymer of the present invention can be used for medical treatment, foods and cosmetics field, exists being applied in of cycloolefin addition polymer to be difficult to (referring to patent documentation 7 to 22) in these fields.In the application in these fields, the solubleness in Permethyl 99A. solvent or siloxane solvent agent preferably is no less than 10wt%, more preferably 30wt%.If less than 10wt%, having, solubleness applies the worry that therefore caudacoria attenuation, film are wanting in anti-cracking or fragility.
The solution that includes the high cycloolefin addition polymer of the gas permeability of invention can be combined with known oxidation inhibitor to improve oxidative stability.
The example of oxidation inhibitor comprises: phenols or hydroquinone compound be as 2,6-two-tertiary butyl-4 methylphenol, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 1; 1 '-two-(4-hydroxy phenyl) hexanaphthene, 2; 5-di-tert-butyl hydroquinone, tetramethylolmethane-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl)] propionic ester etc., phosphorus compound is like three (4-methoxyl groups-3; The 5-phenylbenzene) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate etc., and sulfide compound and lactone cpd.In these compounds, preferably have those (that is, weightlessness is 5% o'clock temperature) of the decomposition temperature that is not less than 250 ℃.The amount of oxidation inhibitor is 0.05 to 5.0 weight part with respect to the cycloolefin addition polymer of the present invention of per 100 weight parts.
Embodiment
Describe the present invention in detail through embodiment and comparative example, but be not to be understood that to only limiting to embodiment.It should be noted that in following formula respectively, Me representes methyl, Ph representes phenyl and Cy representative ring hexyl.
The molecular weight of polymkeric substance, MWD, monomeric proportion of composing, solubleness, second-order transition temperature, breaking tenacity, elongation at break, oxygen permeability coefficient is according to the corresponding evaluation of following method.
The weight-average molecular weight of the polymkeric substance that 1) obtains among the embodiment (Mw), number-average molecular weight (Mn) and MWD (Mw/Mn) use THF to obtain as object of reference as solvent and use PS through GPC.
2) in multipolymer the proportion of composing of norbornene derivative/norbornylene by 1The integration ratio at the peak that H-NMR obtains obtains.
3) solubleness in organic solvent has been used through preparation and has been comprised that Permethyl 99A., methyl three (trimethylsiloxy) silane (hereinafter is abbreviated as M 3T) or the decamethylcyclopentaandoxane (D that is written as hereinafter 5) the 10wt% solution of solvent estimate.
4) second-order transition temperature is measured through using the TMA device, and the sample that will have 100 μ m film thicknesses, 3mm width and 20mm length therein is fixed in probe, begins to heat up from room temperature with the speed of 10 ℃/min.
5) breaking tenacity becomes dumbbell shape with elongation at break No. 2 through the mould with 100 μ m thickness, is fixed in test probe, measures with the speed tractive of 50mm/min.
6) oxygen permeability coefficient uses the disk samples of the film with 50 μ m thickness and 4cm diameter to measure according to pressure differential method.
Embodiment 1
With 0.0115g (2.0 * 10 -5Mole) two (dibenzalacetone) palladium [Pd (C 17H 14O) 2], 0.0184g (2.0 * 10 -5Mole) triphenylcarbenium Four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] and 0.0056g (2.0 * 10 -5Mole) tricyclohexyl phosphine (PCy 3) be dissolved in the toluene of 10ml preparation 2.00 * 10 separately -6The solution of mol/ml.In the Glass Containers that argon gas cleans with 5.210g (13.4 * 10 -3Mole) monomer A and the 0.527g (5.6 * 10 that represent by following formula (6) -3Mole) monomers B (norbornylene) by following formula (7) expression is dissolved in the 5ml toluene.With 1ml each 2.00 * 10 -6The mol/ml catalyst solution joins in the monomer solution of gained, and then at room temperature (21 ℃) carried out polyreaction 20 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (1) of 0.63g (productive rate is 11%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (1) is Mn=805000, and MWD is Mw/Mn=1.67. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=40/60 (moles/mole) of the structure of monomers B.
Figure BSA00000604139200182
Monomer A
Figure BSA00000604139200191
Monomers B
Embodiment 2
Except temperature of reaction being set in 30 ℃, with embodiment 1 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (2) of 3.84g (productive rate is 67%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (2) is Mn=744000, and MWD is Mw/Mn=1.35. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=60/40 (moles/mole) of the structure of monomers B.
Embodiment 3
Except temperature of reaction being set in 40 ℃, with embodiment 1 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (3) of 3.61g (productive rate is 63%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (3) is Mn=699000, and MWD is Mw/Mn=1.54. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=52/48 (moles/mole) of the structure of monomers B.
Embodiment 4
Except temperature of reaction being set in 50 ℃, with embodiment 1 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (4) of 4.36g (productive rate is 76%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (4) is Mn=522000, and MWD is Mw/Mn=1.76. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
Embodiment 5
Except temperature of reaction being set in 70 ℃, with embodiment 1 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (5) of 4.41g (productive rate is 77%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (5) is Mn=285000, and MWD is Mw/Mn=2.51. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=60/40 (moles/mole) of the structure of monomers B.
The result of embodiment 1 to 5 lists in table 1.Fig. 1 to 3 has shown productive rate, molecular weight and the MWD of the polymkeric substance that obtains among the embodiment 1 to 5 and the relation between the temperature of reaction.
Table 1
Figure BSA00000604139200201
Embodiment 6
In the Glass Containers of nitrogen purge, 12.6 (0.04 moles) are dissolved in the 25ml toluene by the represented monomer C of following formula (8).
Figure BSA00000604139200202
Monomer C
(that is, 0.0115g (2.0 * 10 with the catalyst solution for preparing separately -5Mole) two (dibenzalacetone) palladium [Pd (C 17H 14O) 2], 0.0184g (2.0 * 10 -5Mole) triphenylcarbenium
Figure BSA00000604139200203
Four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] and 0.0056g (2.0 * 10 -5Mole) tricyclohexyl phosphine (PCy 3) be dissolved in the solution in the 15ml toluene) add in the monomer solution, then under 30 ℃, carried out polyreaction 2 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (6) of 6.30g (productive rate is 50%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (6) is Mn=935000, and MWD is Mw/Mn=1.77.
Embodiment 7
Except temperature of reaction being set in 60 ℃ and will be set in the reaction times one hour, with embodiment 6 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (7) of 6.05g (productive rate is 48%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (7) is Mn=405000, and MWD is Mw/Mn=1.42.
Comparative example 1
Except using 2.0 * 10 -5Mole is as allyl group cyclopentadienyl moiety the palladium [(C of divalence palladium complex 5H 6) Pd (C 3H 5)] replace outside two (dibenzalacetone) palladiums, with embodiment 6 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (8) of 6.55g (productive rate is 52%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (8) is Mn=632000, and MWD is Mw/Mn=1.40.
Comparative example 2
Except temperature of reaction being set in 60 ℃, will being set in the reaction times 1 hour, with comparative example 1 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (9) of 6.67g (productive rate is 53%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (9) is Mn=641000, and MWD is Mw/Mn=1.41.
Comparative example 3
Except using 2.0 * 10 -5Mole is as two (methyl ethyl diketone) palladium [Pd (C of divalence palladium complex 5H 7O 2) 2] replace outside two (dibenzalacetone) palladiums, with embodiment 6 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (10) of 6.30g (productive rate is 50%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (10) is Mn=1350000, and MWD is Mw/Mn=1.50.
Comparative example 4
Except temperature of reaction being set in 60 ℃, will being set in the reaction times 1 hour, with comparative example 3 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (11) of 5.80g (productive rate is 46%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (11) is Mn=1450000, and MWD is Mw/Mn=1.57.
Embodiment 6 and 7 and the result of comparative example 1 to 4 in table 2, list.Shown among Fig. 4 embodiment 6 and 7 and comparative example 1 to 4 in molecular weight and the relation between the temperature of reaction of the polymkeric substance that obtains.Shown among the embodiment 7 polymer P (7) that obtains among Fig. 6 1H-NMR figure.
Table 2
Embodiment 8
In the Glass Containers of nitrogen purge, 202.4g (0.52 mole) is dissolved in the toluene of 450ml with the monomers B (norbornylene) that 26.4g (0.28 mole) is represented by above-mentioned formula (7) by the monomer A of above-mentioned formula (6) expression.(that is, 0.0115g (2.0 * 10 with the catalyst solution for preparing separately -5Mole) two (dibenzalacetone) palladium [Pd (C 17H 14O) 2], 0.0184g (2.0 * 10 -5Mole) triphenylcarbenium
Figure BSA00000604139200232
Four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] and 0.0056g (2.0 * 10 -5Mole) tricyclohexyl phosphine (PCy 3) be dissolved in the solution in the 15ml toluene) add in the monomer solution, then under 40 ℃, carried out polyreaction 10 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (12) of 153.3g (productive rate is 67%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (12) is Mn=815000, and MWD is Mw/Mn=2.04. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
Embodiment 9
Except temperature of reaction is set in 50 ℃, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (13) of 151.0g (productive rate is 66%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (13) is Mn=601000, and MWD is Mw/Mn=2.41. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=64/36 (moles/mole) of the structure of monomers B.
Embodiment 10
Except temperature of reaction being set in 60 ℃, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (14) of 155.6g (productive rate is 68%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (14) is Mn=351000, and MWD is Mw/Mn=3.86. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=63/37 (moles/mole) of the structure of monomers B.
Embodiment 11
Except temperature of reaction being set in 80 ℃, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (15) of 157.9g (productive rate is 69%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (15) is Mn=225000, and MWD is Mw/Mn=3.78. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=64/36 (moles/mole) of the structure of monomers B.
Embodiment 12
Except temperature of reaction being set in 95 ℃, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (16) of 152.9g (productive rate is 67%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (16) is Mn=162000, and MWD is Mw/Mn=4.11. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
Embodiment 13
In the Glass Containers of nitrogen purge, 404.8g (1.04 moles) is dissolved in the toluene of 900ml with the monomers B (norbornylene) that 52.8g (0.56 mole) is represented by above-mentioned formula (7) by the monomer A of above-mentioned formula (6) expression.(that is, 0.0115g (2.0 * 10 with the catalyst solution for preparing separately -5Mole) two (dibenzalacetone) palladium [Pd (C 17H 14O) 2], 0.0184g (2.0 * 10 -5Mole) triphenylcarbenium
Figure BSA00000604139200251
Four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] and 0.0056g (2.0 * 10 -5Mole) tricyclohexyl phosphine (PCy 3) be dissolved in the solution in the 15ml toluene) join in the monomer solution, then under 55 ℃, carried out polyreaction 10 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (17) of 311.2g (productive rate is 68%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (17) is Mn=564000, and MWD is Mw/Mn=2.43. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=63/37 (moles/mole) of the structure of monomers B.
Comparative example 5
Except using 2.0 * 10 -5Mole is as allyl group cyclopentadienyl moiety the palladium [(C of divalence palladium complex 5H 6) Pd (C 3H 5)] replace outside two (dibenzalacetone) palladiums, with embodiment 10 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (18) of 153.3g (productive rate is 67%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (18) is Mn=569000, and MWD is Mw/Mn=3.05. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
Comparative example 6
Except using 2.0 * 10 -5Mole is as two (methyl ethyl diketone) palladium [Pd (C of divalence palladium complex 5H 7O 2) 2] replace outside two (dibenzalacetone) palladiums, with embodiment 10 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (19) of 157.9g (productive rate is 69%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (19) is Mn=765000, and MWD is Mw/Mn=2.81. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
The result of embodiment 8 to 13 and comparative example 5,6 is shown in the table 3.The molecular weight of each polymkeric substance that obtains among the embodiment 8 to 13 and the relation between the temperature of reaction have been shown among Fig. 5.
Table 3
Figure BSA00000604139200272
Embodiment 14
Will be by 0.0115g (2.0 * 10 -5Mole) two (dibenzalacetone) palladium [Pd (C 17H 14O) 2], 0.0184g (2.0 * 10 -5Mole) triphenylcarbenium
Figure BSA00000604139200273
Four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] and 0.0056g (2.0 * 10 -5Mole) tricyclohexyl phosphine (PCy 3) be dissolved in the solution that obtains in the 15ml toluene and tightly seal, make it place a week.
Next, in the Glass Containers of nitrogen purge, 12.6g (0.04 mole) is dissolved in the 25ml toluene by the represented monomer C of above-mentioned formula (8),, then under 60 ℃, carried out polyreaction 1 hour to wherein adding the said catalyst solution that is placed a week.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (20) of 6.05g (productive rate is 48%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (20) is Mn=485000, and MWD is Mw/Mn=1.51.
The result of the result of embodiment 14 and embodiment 7 is in the lump shown in the table 4.
Table 4
Figure BSA00000604139200281
Comparative example 7
Except using 2.0 * 10 -5Mol is as two (methyl ethyl diketone) palladium [Pd (C of divalence palladium complex 5H 7O 2) 2] replace two (dibenzalacetone) palladiums and with 0.67g (6mmol) 1-octene as outside the molecular weight regulator, with embodiment 10 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (21) of 157.9g (productive rate is 69%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (21) is Mn=379000, and MWD is Mw/Mn=3.69. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=65/35 (moles/mole) of the structure of monomers B.
The result of the result of comparative example 7 and embodiment 8,10 and comparative example 6 is in the lump shown in the table 5
Table 5
Figure BSA00000604139200292
From The above results, can find out following:
1) when use included compound (A), (B) and multicomponent catalyst (C) and prepares cycloolefin addition polymer of the present invention, the molecular weight of the polymkeric substance that obtains can be regulated according to temperature of reaction.
2) when the structure of the siloxanyl monomers of the cycloolefin functionality that change to use during with its feed ratio, the ability of inclusion compound (A), (B) and multicomponent catalyst regulate polymer molecular weight (C) depends on temperature of reaction and keeps.On the other hand, when using existing divalence palladium complex, do not find such ability.
3) include compound (A), (B) and multicomponent catalyst (C) and have high polymerization activity as existing divalence palladium complex.
4) include compound (A), (B) and multicomponent catalyst (C) and have high storage stability.
5) if use the divalence palladium complex, need a large amount of molecular weight regulators suitably to regulate molecular weight.On the other hand, when using 0 valency palladium complex, need not molecular weight regulator.
More especially, about the use of the multicomponent catalyst that forms by compound (A), (B), (C), confirmed ceiling advantage property to cycloolefin addition polymer preparation of the present invention with ad hoc structure.
Embodiment 15
Except using 2.0 * 10 -5Mole four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound replaces triphenylcarbenium as ionic boron cpd
Figure BSA00000604139200301
Outside four (pentafluorophenyl group) borate, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (22) of 148.7g (productive rate is 65%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (22) is Mn=396000, and MWD is Mw/Mn=3.31. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=57/43 (moles/mole) of the structure of monomers B.
Embodiment 16
Except using 2.0 * 10 -5Mole three (dibenzalacetone) two palladium [Pd 2(C 17H 14O) 3] replace two (dibenzalacetone) palladiums and temperature of reaction be set in 50 ℃, will be set in the reaction times outside 20 hours as 0 valency palladium complex, with embodiment 8 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (23) of 146.5g (productive rate is 64%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (23) is Mn=372000, and MWD is Mw/Mn=1.95. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=63/37 (moles/mole) of the structure of monomers B.
Embodiment 17
Except temperature of reaction being set in 30 ℃, with embodiment 16 in same mode carry out polyreaction.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (24) of 141.9g (productive rate is 62%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (24) is Mn=797000, and MWD is Mw/Mn=1.41. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=51/49 (moles/mole) of the structure of monomers B.
Comparative example 8
In the Glass Containers of nitrogen purge, 55.2g (0.142 mole) is dissolved in the toluene of 240ml with the monomers B (norbornylene) that 3.3g (0.035 mole) is represented by above-mentioned formula (7) by the monomer A of above-mentioned formula (6) expression.With separately the preparation catalyst solution (that is, with 23mg (89 μ mol) two (acetoacetyl) nickel [Ni (acac) 2] (bis (acetylacetate) nickel) and 228mg (445 μ mol) three (pentafluorophenyl group) boron [B (C 6F 5) 3] be dissolved in the solution in the 15ml toluene) join in the monomer solution, then under 60 ℃, carried out polyreaction 24 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (25) of 21.6g (productive rate is 37%) in 12 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (25) is Mn=46000, and MWD is Mw/Mn=2.05. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=73/27 (moles/mole) of the structure of monomers B.
Comparative example 9
In the Glass Containers of nitrogen purge, 7.0g (0.018 mole) is dissolved in the toluene of 140ml with the monomers B (norbornylene) that 14.9g (0.159 mole) is represented by above-mentioned formula (7) by the monomer A of above-mentioned formula (6) expression.With separately the preparation catalyst solution (that is, with 23mg (89 μ mol) two (acetoacetyl) nickel [Ni (acac) 2] and 228mg (445 μ mol) three (pentafluorophenyl group) boron [B (C 6F 5) 3] be dissolved in the solution in the 15ml toluene) add monomer solution, then under 25 ℃, carried out polyreaction 2 hours.
After reaction is accomplished, through pouring in a large amount of methyl alcohol, then through filtering separation, washing with under reduced pressure obtained the polymer P (26) of 16.2g (productive rate is 74%) in 6 hours 120 ℃ of dryings with the polymer precipitation that obtains.
When through gpc measurement, the molecular weight of the polymer P that obtains thus (26) is Mn=253000, and MWD is Mw/Mn=2.25. 1The H-NMR stave bright from monomer A structure and from the proportion of composing A/B=8/92 (moles/mole) of the structure of monomers B.
In table 6, show P (7) and the P (25) of P (14) and comparative example 8 and 9 and the solvability of P (26) in embodiment 7 and 10 respectively.
Table 6
Figure BSA00000604139200321
Zero: dissolving, △: be partly dissolved, *: insoluble
The ZGK 5 solvent:
M 3T: methyl three (trimethylsiloxy) silane
D 5: decamethylcyclopentaandoxane
Each all is dissolved in the toluene to prepare the polymers soln of 10wt% with polymer P (7), P (14), P (25) and P (26).According to solution casting method these solution are carried out film forming, then 60 ℃ of dryings 24 hours with preparation polymeric film F (7), F (14), F (25) and F (26).Evaluation result at the film for preparing thus shown in the table 7.
Table 7
Figure BSA00000604139200322
1 crust: 10 -10Cm 3(STP) .cm/cm 2.s.cmHg
Can be found out by above result: solvability, film-forming properties, gas permeability, thermotolerance and the physical strength of the cycloolefin addition polymer with organo-siloxane side chain of the present invention is all excellent, and it can easily prepare through the multicomponent catalyst that use has a particular type structure.
The film-forming properties of the cycloolefin addition polymer that gas permeability according to the present invention is high is excellent, and it has excellent gas permeability, thermotolerance and physical strength.Polymkeric substance of the present invention will be expected to the oxygen permeable membrane as air-conditioning and fuel cell, also can be used as contact lens.In addition, polymkeric substance of the present invention has excellent solvability in organic solvent and ZGK 5 solvent, therefore, be expected to it is applied to medical treatment, foods and cosmetics film.
The high cycloolefin addition polymer of gas permeability according to the present invention can easily prepare through the multicomponent catalyst that use has the excellent polymerization activity of having of particular type structure, selectivity and a molecular-weight adjusting ability.

Claims (7)

1. preparation has high gas permeability and with respect to the method for polystyrene standards by the cycloolefin addition polymer of 100000～2000000 number-average molecular weight (Mn) of gel permeation chromatography; Be included in and comprise the ionic boron compound of (A) 0 valency palladium compound, (B) and exist down with the multicomponent catalyst that (C) has the substituent phosphine compound that is selected from alkyl, cycloalkyl and aryl with 3 to 6 carbon atoms; Addition polymerization is by the cycloolefin functionality siloxanes of the cycloolefin functionality siloxanes of following formula (1) expression or formula (1) with by the mixture of the cyclic olefins of following formula (2) expression; Obtain the cycloolefin addition polymer thus; Wherein the construction unit from the cycloolefin functionality siloxanes of formula (1) is the 10mol% to 100mol% of this addition polymer
Figure FSA00000604139100011
R wherein 1Can be identical or different, and the unit price organic group of expression not fatty family unsaturated link(age), s is 0 to 2 integer, and j is 0 or 1,
Figure FSA00000604139100012
A wherein 1To A 4Independently expression be selected from Wasserstoffatoms, halogen atom, have alkyl, thiazolinyl, naphthenic base, aryl, alkoxyl group, aryloxy and the halo alkyl of 1 to 10 carbon atom group, or be selected from the polar group of oxetanyl and carbalkoxy, condition is A 1And A 2Perhaps A 1And A 3Can form alicyclic structure, aromatic ring structure, carbimide group or anhydride group with the carbon atom of their institute's bondings, and i is 0 or 1.
2. method according to claim 1; Wherein compound (A) is: being two (dibenzalacetone) palladiums of the complex compound that cooperates with one 0 valency palladium atom of two dibenzalacetone molecules, perhaps is three (dibenzalacetones), two palladiums of the complex compound of three dibenzalacetone molecules and two 0 valency palladium atoms; Compound (B) is triphenylcarbenium four (pentafluorophenyl group) borate or four (pentafluorophenyl group) lithium tetraborate-ethyl ether complex compound, and compound (C) is a tricyclohexyl phosphine.
3. method according to claim 1, the R in its Chinese style (1) 1Be methyl.
4. method according to claim 1, the A in its Chinese style (2) 1To A 4Represent Wasserstoffatoms independently, and i is 0.
5. method according to claim 1, wherein this addition polymerization is carried out under the condition of 0 to 150 ℃ and 1 to 72 hour in non-active gas atmosphere.
6. method according to claim 1; Wherein calculate with 0 valency palladium; Compound (A) is with respect to the monomeric total amount of every mole of formula (1) and formula (2); Use with 1/1000000 to 1/100 mole amount, compound (B) uses with 1.0 to 2.0 moles amount with respect to every mole compound (A), and compound (C) uses with 0.25 to 2.0 mole amount with respect to every mole compound (A).
7. method according to claim 1, wherein addition polymerization is carried out in solvent, and wherein the amount S of solvent representes the scope 0.1 to 30 with the weight ratio of the total amount M of the cycloolefin monomers of being made up of the compound of formula (1) and formula (2) with S/M.
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CN101282982A (en) * 2005-10-05 2008-10-08 Lg化学株式会社 Catalysts for polymerizing cyclic olefin
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